| 1. |
- Ryan, Hugh P., et al.
(författare)
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Quantifying the Effect of Guest Binding on Host Environment
- 2023
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Ingår i: Journal of the American Chemical Society. - 1520-5126 .- 0002-7863. ; 145:36, s. 19533-19541
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Tidskriftsartikel (refereegranskat)abstract
- The environment around a host-guest complex is defined by intermolecular interactions between the complex, solvent molecules, and counterions. These interactions govern both the solubility of these complexes and the rates of reactions occurring within the host molecules and can be critical to catalytic and separation applications of host-guest systems. However, these interactions are challenging to detect using standard analytical chemistry techniques. Here, we quantify the hydration and ion pairing of a FeII4L4 coordination cage with a set of guest molecules having widely varying physicochemical properties. The impact of guest properties on host ion pairing and hydration was determined through microwave microfluidic measurements paired with principal component analysis (PCA). This analysis showed that introducing guest molecules into solution displaced counterions that were bound to the cage, and that the solvent solubility of the guest has the greatest impact on the solvent and ion-pairing dynamics surrounding the host. Specifically, we found that when we performed PCA of the measured equivalent circuit parameters and the solubility and dipole moment, we observed a high (>90%) explained variance for the first two principal components for each circuit parameter. We also observed that cage-counterion pairing is well-described by a single ion-pairing type, with a one-step reaction model independent of the type of cargo, and that the ion-pairing association constant is reduced for cargo with higher water solubility. Quantifying hydration and cage-counterion interactions is a critical step to building the next generation of design criteria for host-guest chemistries.
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| 2. |
- Aakeröy, Christer, et al.
(författare)
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Co-crystal screening of diclofenac
- 2011
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Ingår i: Pharmaceutics. - : MDPI AG. - 1999-4923. ; 3:3, s. 601-614
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Tidskriftsartikel (refereegranskat)
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| 3. |
- Canton, Martina, et al.
(författare)
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Improving Fatigue Resistance of Dihydropyrene by Encapsulation within a Coordination Cage
- 2020
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 142:34, s. 14557-14565
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Tidskriftsartikel (refereegranskat)abstract
- Photochromic molecules undergo reversible isomerization upon irradiation with light at different wavelengths, a process that can alter their physical and chemical properties. For instance, dihydropyrene (DHP) is a deep-colored compound that isomerizes to light-brown cyclophanediene (CPD) upon irradiation with visible light. CPD can then isomerize back to DHP upon irradiation with UV light or thermally in the dark. Conversion between DHP and CPD is thought to proceed via a biradical intermediate; bimolecular events involving this unstable intermediate thus result in rapid decomposition and poor cycling performance. Here, we show that the reversible isomerization of DHP can be stabilized upon confinement within a (PdIIL4)-L-6 coordination cage. By protecting this reactive intermediate using the cage, each isomerization reaction proceeds to higher yield, which significantly decreases the fatigue experienced by the system upon repeated photocycling. Although molecular confinement is known to help stabilize reactive species, this effect is not typically employed to protect reactive intermediates and thus improve reaction yields. We envisage that performing reactions under confinement will not only improve the cyclic performance of photochromic molecules, but may also increase the amount of product obtainable from traditionally low-yielding organic reactions.
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| 4. |
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| 5. |
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| 6. |
- Grommet, Angela Beth, 1991, et al.
(författare)
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Chemical Reactivity Under Nanoconfinement
- 2020
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Ingår i: Nature Nanotechnology. - : Springer Science and Business Media LLC. - 1748-3387 .- 1748-3395. ; 15:4, s. 256-271
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Forskningsöversikt (refereegranskat)
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| 7. |
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| 8. |
- Grommet, Angela Beth, 1991, et al.
(författare)
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Molecular Photoswitching in Confined Spaces
- 2020
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Ingår i: Accounts of Chemical Research. - : American Chemical Society (ACS). - 0001-4842 .- 1520-4898. ; 53:11, s. 2600-2610
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Forskningsöversikt (refereegranskat)
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| 9. |
- Kuntrapakam, Hema, et al.
(författare)
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Guest Encapsulation Alters the Thermodynamic Landscape of a Coordination Host
- 2023
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Ingår i: Journal of the American Chemical Society. - 1520-5126 .- 0002-7863. ; 145:45, s. 24755-24764
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Tidskriftsartikel (refereegranskat)abstract
- The architecture of self-assembled host molecules can profoundly affect the properties of the encapsulated guests. For example, a rigid cage with small windows can efficiently protect its contents from the environment; in contrast, tube-shaped, flexible hosts with large openings and an easily accessible cavity are ideally suited for catalysis. Here, we report a “Janus” nature of a Pd6L4 coordination host previously reported to exist exclusively as a tube isomer (T). We show that upon encapsulating various tetrahedrally shaped guests, T can reconfigure into a cage-shaped host (C) in quantitative yield. Extracting the guest affords empty C, which is metastable and spontaneously relaxes to T, and the T⇄C interconversion can be repeated for multiple cycles. Reversible toggling between two vastly different isomers paves the way toward controlling functional properties of coordination hosts “on demand”.
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| 10. |
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